Rapid growth in the demand for lithium-ion batteries (LIBs) has surged the amount of hazardous waste generated in recent years. Recycling of spent LIBs is important from the economic and environmental point of view. NMC type of spent LIBs cathode powders include Li, Co, Ni and Mn in different stoichiometric ratios. The effect of temperature, oxalic acid concentration, stirring speed, particle size and solid/liquid ratio on the leaching of Li, Co, Ni and Mn from NMC 111 type of cathode powder was investigated in this work. It was determined that leaching behavior of Li and Mn is different than that of Co and Ni. While 79% of Li and 84% of Mn extracted in oxalic acid solution, leached Co and Ni precipitated as CoC2O4∙2H2O and NiC2O4∙2H2O. Oxalates with cubic or plate-like morphology were obtained depending on the leaching temperature. Shrinking Core Model was used to analyze experimental data obtained. Apparent activation energy (E) was calculated as 14.049 kJ mol−1 indicating that leaching reaction is controlled by diffusion while order of concentration (m) was found to be as 0.15 for the leaching of Li. Model kinetic equation which gives the change of XLi as a function of time was obtained using all kinetic parameters determined and is shown as follows:<InlineEquation ID="IEq1"> <EquationSource Format="TEX">$X_{Li} = 1 {-} \left[ {1 {-} 0.0139 C_{o}^{0.15} \exp \left( {{-} \frac{14049}{{8.314T}}} \right)t} \right]^{3}$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <msub> <mi>X</mi> <mrow> <mi mathvariant="italic">Li</mi> </mrow> </msub> <mo>=</mo> <mn>1</mn> <mo>-</mo> <msup> <mfenced close="]" open="["> <mrow> <mn>1</mn> <mo>-</mo> <mn>0.0139</mn> <msubsup> <mi>C</mi> <mrow> <mi>o</mi> </mrow> <mrow> <mn>0.15</mn> </mrow> </msubsup> <mo>exp</mo> <mfenced close=")" open="("> <mrow> <mo>-</mo> <mfrac> <mn>14049</mn> <mrow> <mn>8.314</mn> <mi>T</mi> </mrow> </mfrac> </mrow> </mfenced> <mi>t</mi> </mrow> </mfenced> <mn>3</mn> </msup> </mrow> </math></EquationSource> </InlineEquation>NMC 111 type of cathode powder which includes LiCo0.333Ni0.333Mn0.333O2, LiNi0.5Mn1.5O4 and Li2MnO3 phases was successfully produced by a facile and practical method. Graphic Abstract

Investigation of Leaching Kinetics of Spent Lithium-Ion Battery Cathode Material in Oxalic Acid Solution and Production of NMC 111 Cathode Powder

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发表日期：

2025年8月26日

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Safiye Tanriverdi Terzioğlu,
Sedat Ilhan

摘要

Rapid growth in the demand for lithium-ion batteries (LIBs) has surged the amount of hazardous waste generated in recent years. Recycling of spent LIBs is important from the economic and environmental point of view. NMC type of spent LIBs cathode powders include Li, Co, Ni and Mn in different stoichiometric ratios. The effect of temperature, oxalic acid concentration, stirring speed, particle size and solid/liquid ratio on the leaching of Li, Co, Ni and Mn from NMC 111 type of cathode powder was investigated in this work. It was determined that leaching behavior of Li and Mn is different than that of Co and Ni. While 79% of Li and 84% of Mn extracted in oxalic acid solution, leached Co and Ni precipitated as CoC₂O₄∙2H₂O and NiC₂O₄∙2H₂O. Oxalates with cubic or plate-like morphology were obtained depending on the leaching temperature. Shrinking Core Model was used to analyze experimental data obtained. Apparent activation energy (E) was calculated as 14.049 kJ mol⁻¹ indicating that leaching reaction is controlled by diffusion while order of concentration (m) was found to be as 0.15 for the leaching of Li. Model kinetic equation which gives the change of X_Li as a function of time was obtained using all kinetic parameters determined and is shown as follows:

$X_{Li} = 1 {-} \left[ {1 {-} 0.0139 C_{o}^{0.15} \exp \left( {{-} \frac{14049}{{8.314T}}} \right)t} \right]^{3}$ $X_{Li} = 1 - {[1 - 0.0139 C_{o}^{0.15} exp (- \frac{14049}{8.314 T}) t]}^{3}$

NMC 111 type of cathode powder which includes LiCo_0.333Ni_0.333Mn_0.333O₂, LiNi_0.5Mn_1.5O₄ and Li₂MnO₃ phases was successfully produced by a facile and practical method.

Graphic Abstract